Preparation of resinous reaction products of sulphur dioxide and olefins



patented o ct. 14, i4i

PREPARATION OF RESINOUS REACTION PRODUCTS F SULPHUR DIOXIDE AND OLEFINS Frederick E. Frey, Bartlesville, 0kla., and Louis H. Fitch,J1'., deceased, late of Bartlesville, 0kla., byFirst National Bank of Bartlesville, administrator, Bartlesville, 0kla., assignors to Phillips Petroleum Company, Bartlesville, 0kla., a corporation of Delaware Ne Drawing. Original application March 16,

1932, Serial No. 599,350. Divided and this application September 6, 1938, Serial No. 228,705

9 Claims.

The present invention relates to the catalytic preparation of resinous reaction products of sulphur dioxide and olefins, and to catalysts for effecting such reactions. The invention also relates to a method-of molding the solid products of the olefin-sulphur dioxide reaction.

The present application is a division of our co-pending application Serial Number 599,350, filed March 16, 1932, now Patent No. 2,128,932.

with one-half of one percent by weight of benzoyl peroxide in solution. The reagents were completely converted into a solid resin on standing for three days in the dark at 80 F. Under the same conditions, in the absence of a catalyst,

2-butene and sulphur dioxide failed to react-to.

any appreciable extent in the course of. three months.

With the same materials and conditions, small quantities of another peroxide, diethyl peroxide,

A primary object of the invention is the pro- 10 induced the complete conversion of the reagents vision of catalysts adapted to enhance the reto resin in four days. Small quantities of silver action between sulphur dioxide and olefins, and nitrate induced the reaction to completion in to cause such reaction to take place rapidly even thirty minutes. in complete darkness. The aforementioned catalysts have been found A further object of the invention is the proviuseful in inducing and accelerating the reaction sion of a heat-pressure molding process for the of other olefins' such as ethylene, propylene, production of coherent resinous products from butene-l, pentene-l, hexene-l, heptene-l, and the reaction products of sulphur dioxide and isopropyl ethylene, with sulphur dioxide both in folefins. the presence and absence of light and diluents.

Additional objects will become apparent as the The reaction of diolefins such as 1,3-butadiene description of the invention proceeds. and cyclopentadiene with sulphur dioxide is like- While the reaction between sulphur dioxid wise accelerated by these catalysts. and certain olefins to form a resin-like product The products obtained when using the cataisknown, the reaction as therein described, takes lysts are similar to those obtained when the place readily only in the presence of sunlight or reaction is carried out in the presence of light some other source of actinic light. alone. In some cases, however, they mayexhibit Heat alone has been found to be of but limited difierences in softening temperatures and other effectiveness in bringing about interaction bephysical characteristics, these differences being tween sulphur dioxide and olefins to form 2. apparently due to difierences in the stage of resin-like product. Many olefins which react polymerization of the product, and not to the rapidly with sulphur dioxide in the presence of inclusion of the catalyst in the. product. as an light, do not react readily in the dark, even'at impurity. Regardless of how produced, they temperatures somewhat in excess of 100 C. usually form as a glassy, viscous material in the According to the present invention, the reacpresence of an excess of sulphur dioxide which tion can be made to take place in complete darkdissolves the resin, except in the case of ethylene, ness in the presence of small amounts of chemical propylene and some dienes, which yield a resin agents which exert a catalytic efiect. It has been insoluble in sulphur dioxide.

found that by the addition of suitable catalysts. The polymerization of these materials is not the preparation of resinous reaction products of primarily a reaction at the surface of the catasulphur dioxide and olefins may be efiected at 40 lyst, but is principally due to the presence of low temperatures in comparatively short reaction catalyst dissolved in the olefin, S02 mixture. times, and in the absence-of means for providing Consequently, any means by which the olefin actinic light. The catalysts, however, are also sulphur dioxide, and catalyst maybe mixed propeffective in conjunction with elevated temperaerly, and held at the requisite temperature for tures and/or light. 4 a sufiicient period of time, is'satisfactory for the The catalysts which are suitable for catalyzing formation of the product. the reaction between sulphur dioxide and oleflns In molding resins obtained in either of the under the conditions outlined are oxygen, organic ways indicated in the preceding paragraph, cerperoxides, salts of silver and monovalent copper, tain difliculties are encountered. The resinous nitric oxide, and nitrogen dioxide. Silver sulmaterials can be melted under ordinarycondiphate and sulphite also catalyze the reaction. tions only with considerable swelling and decom- Cuprous chloride is a catalyst for the reaction. position, and hence cannot be formed into useful For example, Z-butene and sulphur dioxide shapes by melting and pouring into molds. The

were sealed in liquid mixture in a glass tube formation of the resin in the mold, either in the presence or .absence of pressure substantially attests drying or in other suitable manner), and treated I in a mold under suitable conditions of heat and pressure, products of very valuable properties may be produced.

The resins produced from the reaction of 1- butene, 2-butene or similar olefins with liquid sulphur dioxide may, for example, be heated in granularform to temperatures of 110 C. to 170 C. in a mold under pressures of 200 to 2000 or more pounds per square inch to produce a vitreous transparent or semi-transparent coherent body of good mechanical strength and hardness.

Similarly, the resin produced from prorylene and liquid sulphur dioxide, which separates as an insoluble powder from the reaction mixture, may be heated to temperatures of 150 C. to 240 C. in a mold under pressure to produce a very hard vitreous body varying from opaque to transparent according to conditions of temperature and pressure. High pressures favor the formation of well fused, transparent and transulcent bodies, though the pressures necessary for this purpose vary greatly with the difierent resins.

In the two foregoing examples, the l-butene resin may be molded into a transparent product at suitable temperatures under pressuresaround 200 pounds per square inch, whereas the propylene resin may generally be more advantageously molded at 2000 pounds per square inch or over.

In general, the mold is cooled before releasing I the pressure and removing the product, but by the selection of the lower molding temperatures and pressures sufficient for the resin under treatment, this cooling may be avoided and the resin removed from the mold at molding temperature.

The duration of the heat treatment is not usually of primary importance, as in the case of phenol-formaldehyde resins, though it should be long enough to enable all the resin to come to a fairly uniform temperature, and short enough to avoid serious decomposition of the resin. The resin may, however, usually be heated to molding temperature prior to the application of pressure without serious decomposition. If the resin to be molded has been heated to moldingtemperature prior to the application of pressure, the time required to produce a coherent resin of desired properties need usually not exceed the time required to develop the desired pressure and, in some cases, cool the mold somewhat. The molding process appears to depend predominantly on a softening or partial fusion under pressure, though further polymerization during the application of heat may also contribute to the formation of a satisfactory product. The application of pressure is necessary not merely for the shap- The nature of the molded products is dependent upon both the nature of the original material and. the conditions of heat and pressure treatment. In general, they are colorless or slightly brown, and quite hard and tough, but may be either opaque, translucent or highly transparent. The resin may be compounded with fillers, dyes, pigments and the like to produce desired variations in mechanical properties and appearance.

The molded products are similar chemically to the material used for molding. They are not readily attacked by acids, alkalis or halogens, and are insoluble in most solvents, although liquid sulphur dioxide is a good solvent for most of them. The products are suitable for a wide variety of uses.

What is claimed:

1.The method of producing high molecular weight heteropolymers of sulphur dioxide and olefins which comprises reacting olefins with sulphur dioxide in the presence of a salt of monovalent copper.

2. The method of accelerating the reaction between olefins and sulphur dioxide to produce high molecular weight heteropolymers which comprises reacting olefins with sulphur dioxide in the presence of a salt of monovalent copper.

3. The method of producing high molecular weight reaction products of olefins and. sulphur dioxide in the absence of actinic light which comprises conducting the reaction in the presence of a salt of monovalent copper.

4. The method of accelerating the reaction between olefins and sulphur dioxide to produce high molecular weight heteropolymers, which comprises conducting the reaction in the presence of cuprous chloride.

5. The method of producing high molecular weight products of the reaction between sulphur dioxide and olefins in the absence of actinic light which comprises incorporating in the reaction mixture 2. small quantity of cuprous chloride.

6. The method of producing high molecular weight heteropolymers of sulphur dioxide and olefins, which comprises reacting olefins with sulphur dioxide in the presence of a cuprous halide.

7. In the process of producing high molecular weight heteropolymers of sulphur dioxide and olefin, the method of conducting the reaction in the absence of suflicient actinic light to effect the reaction or promote the reaction at a satisfactory rate which comprises conducting the reaction in the presence of a catalyst comprising a salt -of monovalent copper.

8. The process as in claim 7 in which the salt of monovalent copper is a halide.

9. The method of claim 7 in which the salt 0! monovalent copper is cuprous chloride.

FIRST NATIONAL BANK IN BARTLESVIIIE. Administrator of the Estate of Louis H. Fitch,

Jr., Deceased,

By J. F. CRONIN,

Vice-President.

FREDERICK E. FREY. 

